Red phosphor

ABSTRACT

The present disclosure provides a red phosphor represented by formula (1): 
       (x-a-b)MgO.aM 1 O.bM 2 O 1.5 .yMgF 2 .fM 6 X 2 .(1-g)GeO 2 .gM 7 O 1.5 :zMn 4+   (1)
 
     where x, y, z, a, b, f, and g satisfy 1.144≦x≦11.0, 0&lt;y&lt;1.597, 0&lt;z&lt;0.1, 0&lt;a&lt;1.0, 0≦b≦1.0, 0≦f≦2.0, 0≦g&lt;0.484, 1.144&lt;(x-a-b), and b and g satisfy b+g≠0; M 1  is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn; M 2  is at least one element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; M 6  is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn; M 7  is at least one element selected from the group consisting of B, Al, Ga, and In; and X is at least one element selected from the group consisting of F, Cl, Br, and I, and M 6 X 2  is other than MgF 2 .

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to Japanese Patent Application No. 2015-014567, filed on Jan. 28, 2015, and No. 2015-140779 filed on Jul. 14, 2015. The entire disclosure of Japanese Patent Application No. 2015-014567 and No. 2015-140779 are hereby incorporated herein by reference.

BACKGROUND

1. Technical Field

The present disclosure relates to a red phosphor.

2. Description of the Related Art

A light -emitting diode is a semiconductor light emitting element produced from a metal compound such as gallium nitride (GaN). Combining such a semiconductor light emitting element and a phosphor, various light emitting devices to emit light of a while color, an incandescent lamp color, an orange color and so on have been developed. Those light emitting devices to emit a white light and so on can be obtained based on the principle of light-color mixing. As for the system to emit a white light, there are known systems such as a system which employs an ultraviolet-light emitting element and three types of phosphors which emit lights of a red color (R), green color (G), and blue color (B), respectively, and a system which employs a blue-light emitting element and a yellow-light emitting phosphor. Light emitting devices of the type which employ a blue-light emitting element and a phosphor to emit yellow light etc., are in demand in a wide range of fields such as general lighting, on-vehicle lighting, displays, backlights for liquid crystal devices. Of those, for the phosphors used for backlights for liquid crystal, in order to reproduce a wide range of colors on a chromaticity diagram, high color purity is also demanded along with the light emitting efficiency. Particularly, the phosphors used for backlights for liquid crystal devices are required to have compatibility in combination with a filter, and a phosphor with a narrow half width of the emission peak has been in demand.

For example, as for red phosphors having an excitation band in blue-region and an emission peak with a narrow half width, fluoride phosphors having compositions such as K₂SiF₆:Mn⁴⁺, K₂TiF₆Mn⁴⁺, K₂SnF₆Mn⁴⁺, Na₂TiF₆:Mn⁴⁺, Na₂ZrF₆:Mn⁴⁺, K₂Si_(0.5)Ge_(0.5)F₆:Mn⁴⁺ etc., are described in published Japanese translation of PCT international publication for patent application No. 2009-528429.

As for a red phosphor having an emission peak with a narrow half width, a phosphor (hereinafter may be referred to as a “MGF phosphor”) having a composition formula of 3.5 MgO 0.5 MgF₂ GeO₂:Mn⁴⁺ is known. The MGF phosphors are known as red phosphors that are excited by light having a wavelength of about 254 nm from a mercury lamp. The MGF phosphors can be formed through calcination at about 1200° C., under atmospheric pressure, and thus have an advantage of facilitating manufacturing.

In Japanese unexamined patent publication No. 2008-202044, a red phosphor is described in which MgF₂ in a MGF phosphor is entirely substituted by AF₂ (A is Ca, Sr, Ba, or Zn, or a mixture of those). Also, in Example 3 in Japanese unexamined patent publication No. 2008-202044, a red phosphor is described in which a luminous efficiency excited by light of a wavelength of 400 nm is improved to a maximum of 143% compared to that of the MGF phosphor.

A MGF phosphor has a high luminous efficiency when excited by light having a wavelength of about 254 nm from a mercury lamp. Meanwhile, the luminous efficiency of the MGF phosphor tends to decrease when excited by light having a wavelength in a range of 350 to 500 nm.

SUMMARY

Accordingly, an aim of one embodiment of the present disclosure is to provide a red phosphor that has fundamental properties of a MGF phosphor and exhibits a high luminous efficiency when excited by light having a wavelength in a range of 350 to 500 nm.

The inventor of the present invention has solved the above disadvantage by substituting a portion of the constituent elements of a MGF phosphor by other elements.

The present disclosure includes embodiments as described below.

A red phosphor represented by formula (1):

(x-a-b)MgO.aM¹O.bM²O_(1.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (1)

-   -   where x, y, z, a, b, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597,         0<z<0.1, 0≦b≦1.0, 0<f2.0, 0≦g<0.484, 1.144<(x-a-b) and further,         b and g satisfy b+g≠0;     -   M¹ is at least one element selected from the group consisting of         Ca, Sr, Ba, and Zn;     -   M² is at least one element selected from the group consisting of         Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,         and Lu;     -   M⁶ is at least one element selected from the group consisting of         Mg, Ca, Sr, Ba, and Zn;     -   M⁷ is at least one element selected from the group consisting of         B, Al, Ga, and In; and     -   X is at least one element selected from the group consisting of         F, Cl, Br, and I; and     -   where M⁶X₂ is other than MgF₂.

The present disclosure includes embodiments as described below.

A red phosphor represented by formula (2):

(x-b)MgO.bM²O_(1.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (2)

-   -   where x, y, z, b, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597,         0<z<0.1, 0≦b≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-b), and further,         b and g satisfy b+g≠0;     -   M² is at least one element selected from the group consisting of         Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,         and Lu;     -   M⁶ is at least one element selected from the group consisting of         Mg, Ca, Sr, Ba, and Zn;     -   M⁷ is at least one element selected from the group consisting of         B, Al, Ga, and In; and     -   X is at least one element selected from the group consisting of         F, Cl, Br, and I; and     -   where M⁶X₂ is other than MgF₂.

The present disclosure includes embodiments as described below.

A red phosphor represented by formula (3):

(x-c)MgO.cM³O_(0.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (3)

-   -   where x, y, z, c, f, and g satisfy 1.144≦x≦11.0; 0<y<1.597,         0<z<0.1, 0<c≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-c);     -   M³ is at least one element selected from the group consisting of         Li, Na, and K;     -   M⁶ is at least one element selected from the group consisting of         Mg, Ca, Sr, Ba, and Zn;     -   M⁷ is at least one element selected from the group consisting of         B, AL, Ga, and In; and     -   X is at least one element selected from the group consisting of         F, Cl, Br, and I; and     -   where M⁶X₂ is other than MgF₂.

The present disclosure includes embodiments as described below.

A red phosphor represented by formula (4):

(x-d)MgO.dM⁴O_(2.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (4)

-   -   where x, y, z, d, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597,         0<z<0.1, 0<d≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-d);     -   M⁴ is at least one element selected from the group consisting of         V, Nb, and Ta;     -   M⁶ is at least one element selected from, the group consisting         of Mg, Ca, Sr, Ba, and Zn;     -   M⁷ is at least one element selected from the group consisting of         B, Al, Ga, and In; and     -   X is at least one element selected from the group consisting of         F, Cl, Br, and I; and     -   where M⁶X₂ is other than MgF₂.

The present disclosure includes embodiments as described below.

A red phosphor represented by formula (5):

(x-e)MgO.eM⁵O₃.yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (5)

-   -   where x, y, z, e, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597,         0<z<0.1, 0<e≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-e);     -   M⁵ is at least one element selected from the group consisting of         Cr, Mo, and W;     -   M⁶ is at least one element selected from the group consisting of         Mg, Ca, Sr, Ba, and Zn:     -   M⁷ is at least one element selected from the group consisting of         B, Al, Ga, and In; and     -   X is at least one element selected from the group consisting of         F, Cl, Br, and I; and     -   where M⁶X₂ is other than MgF₂.

According to the embodiments described above, a red phosphor that has fundamental properties of a MGF phosphor and exhibits a high luminous efficiency when excited by light having a wavelength in a range of 350 to 500 nm can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram showing emission spectra of the phosphors according to Example 12, Comparative Example 1, and Reference Example.

FIG. 2 is a diagram showing excitation spectra of the phosphors according to Examples 3, 8, and 12 and Comparative Example 1.

FIG. 3 is a diagram showing relative energies of phosphors according to one embodiment of the present disclosure.

DETAILED DESCRIPTION OF EMBODIMENT

Certain embodiments according to the present disclosure will be described below. The embodiments shown below are intended as illustrative of a red phosphor and a light emitting device using the same to give a concrete form to technical ideas of the present invention, and the scope of the invention is not limited to those described below.

In the specification, the relation between the color names and the chromaricity coordinates, the relation between the ranges of wavelength of light and the color names of single color light, and the like conform to JIS Z8110. More specifically, the wavelengths of 380 nm to 410 nm correspond to purple light, 410 nm to 455 nm correspond to blue purple light, 455 nm to 485 nm correspond to blue light, 485 nm to 495 nm correspond to blue green light, 495 nm to 548 nm correspond to green light, 548 nm to 573 nm correspond to yellow green light, 573 nm to 584 nm correspond to yellow light, 584 nm to 610 nm correspond to yellow red light, and 610 nm to 780 nm correspond to red light.

In the specification, the term “process” refers not only an independent process but also a process which is indistinguishable from other processes but which can achieve an intended purpose. Also, a numerical range indicated using “to” in the present specification represents a range including numerical values described before and after “to” as a minimum value and a maximum value, respectively. Further, the content of each component in the composition indicates that in the case where a plural number of substances corresponding to each component are present in the composition, refers to a total amount of the plural number of substance in the composition.

The inventor of the present invention discovered that a red phosphor obtained by substituting a portion of MgF₂ in the composition of a MGF phosphor by M⁶X₂ (a compound in which M⁶ is Mg, Ca, Sr, Ba, or Zn, and X is F, Cl, Br, or I), and also substituting a portion of Mg of MgO in the composition of the MGF phosphor by M¹ (Ca, Sr, Ba, or Zn), M²(Sc, Y, La, Ge, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu), M³ (Li, Na, or K), M⁴ (V, Nb, or Ta), or M⁵ (Cr, Mo, or W), or substituting a portion of Ge of GeO₂ in the composition of a MGF phosphor by M⁷ (B, Al, Ga, or In) has a luminous efficiency higher than the luminous efficiency of the MGF phosphor. Further, the inventor of the present invention discovered that some of the red phosphors obtained by substituting a portion of MgF₂ in the composition of a MGF phosphor by M⁶X₂, substituting a portion of Mg of MgO in the composition of a MGF phosphor by M² or M² and M¹, substituting a portion of Ge of GeO₂ in the composition of a MGF phosphor by M⁷, have a luminous efficiency at a wavelength range of 600 to 670 nm exceeding 200% with respect to the luminous efficiency of the MGF phosphor.

Details of the first red phosphor to the fifth red phosphor will be described below.

Red Phosphor

First Red Phosphor

A first red phosphor can be represented by following formula (1):

(x-a-b)MgO.aM¹O.bM²O_(1.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (1)

-   -   where x, y, z, a, b, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597,         0<z<0.1, 0≦b≦1.0, 0<f2.0, 0≦g<0.484, 1.144<(x-a-b) and further,         b and g satisfy b+g≠0;     -   M¹ is at least one element selected from the group consisting of         Ca, Sr, Ba, and Zn;     -   M² is at least one element selected from the group consisting of         Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,         and Lu;     -   M⁶ is at least one element selected from the group consisting of         Mg, Ca, Sr, Ba, and Zn;     -   M⁷ is at least one element selected from the group consisting of         B, Al, Ga, and In; and     -   X is at least one element selected from the group consisting of         Ca, Sr, Ba, and Zn; and     -   where M⁶X₂ is other than MgF₂.

In the formula (1), the variables a, b, f, and g satisfy 0<a<1.0, 0≦b≦1.0, 0<f≦2.0, and 0≦g<0.484, and further, b and g satisfy b+g≠0. That is, the first red phosphor has a MGF-phosphor composition in which MgF₂ is partially substituted by M⁶X₂, a portion of Mg in MgO is substituted by M¹, a portion of Mg in MgO is substituted by M², and/or a portion of Ge in GeO₂ is substituted by M⁷.

aM¹O

M¹O is a component for partially substituting MgO. M¹ is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, in which Ca, Sr, or Zn is preferable. The variable a preferably satisfies 0<a< 1.0, and preferably satisfies 0.094≦a≦0.462. With the variable a satisfying 0.094≦a≦0.462, the luminous efficiency can be further increased.

bM²O_(1.5)

M²O_(1.5) is a component for partially substituting MgO. M² is at least one element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu, in which Sc or Lu is preferable and Sc is more preferable. The variable b satisfies 0≦b≦1.0. The variable preferably satisfies 0<b≦1.0, and more preferably satisfies 0<b≦0.495. Thus, it is more preferable that M² is Sc and b satisfies 0<b≦0.495. Further, it is more preferable that with the variable b satisfying 0.001≦b≦0.320, more preferably satisfying 0.006≦b≦0.320, the luminous efficiency can be further increased.

Variable x

The variable x satisfies 1.144≦x≦11.0. The variable x represents a total amount of the MgO site in the red phosphor. The variable x preferably satisfies 2.422≦x≦5.189. With the variable x satisfying 2.925≦x≦3.1, the luminous efficiency can be further increased and thus more preferable. In the first red phosphor, the variables x, a, and b satisfy 1.144<(x-a-b) and preferably satisfy 2.422≦(x-a-b)≦5.189. With (x-a-b) equal or smaller than 1.144, an excessive amount of M¹O or M¹O and M²O_(1.5) is substituted in the MgO site, resulting in a small luminous efficiency.

Variable y

The variable y represents the amount of MgF₂. The variable y satisfies 0<y<1.597. With the variable y exceeding 1.597, an excess amount of MgF₂ is provided, resulting in a low luminous efficiency. Meanwhile, with the variable y of zero, properties typically to a MGF phosphor cannot be exhibited, resulting in a low luminous efficiency. Thus, the variable y preferably satisfies 0.160≦y≦1.213. With the variable y satisfying 0.403≦y≦0.856, the luminous efficiency can be further increased and thus more preferable.

fM⁶X₂

M⁶X₂ is a component for partially substituting MgF₂. M⁶ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn, in which Ca, Sr, Ba or Zn is preferable, and Ca is more preferable. X is at least one element selected from the group consisting of F, Cl, Br, and I, in which Cl or Br is preferable and Cl is more preferable. M⁶X₂ is preferably MgCl₂, CaCl₂, SrCl₂, BaCl₂, ZnCl₂, MgBr₂, or CaBr₂, and CaCl₂ is more preferable. That is, it is more preferable that M⁶ is Ca and X is Cl.

The variable f satisfies 0<f≦2.0, preferably satisfies 0<f≦1.472, and more preferably satisfies 0<f<1.472. With the variable f satisfying 0.296≦f≦0.852, the luminous efficiency can be further increased and thus more preferable.

In the case where M⁶X₂ is not CaCl₂, the variable f satisfying 0<f≦0.210, the luminous efficiency can be further increased and thus more preferable.

As for the variables y and f, “y+f” correspond to a total amount of MgF₂ site in the MGF phosphor. The variables y and f satisfy 0<y+f<3.597, preferably satisfy 0<y+f≦3.0, and more preferably satisfy 0<y+f≦2.25.

gM⁷O_(1.5)

gM⁷O_(1.5) is a component for substituting GeO₂. M⁷ is at least one element selected from the group consisting of B, Al, Ga, and In, and In or Ga is preferable and Ga is more preferable. The variable g satisfies 0≦g<0.484, preferably satisfies 0<g≦0.295, and more preferably satisfies 0.003≦g≦0.295. Thus, it is preferable that M⁷ is Ga and g satisfies 0<g≦0.295, and it is more preferable that M⁷ is Ga and g satisfies 0.003≦g≦0.295. Further, with the variable g satisfying 0.035≦y≦0.093, the luminous efficiency can be further increased and thus more preferable.

Variable z

The variable z represents an amount of Mn⁴⁺. The variable z satisfies 0<z<0.1. With the variable z 0.1 or greater, an excessive amount of Mn⁴⁺ is provided, resulting in a significant decrease in the luminous efficiency. Thus, the variable z preferably satisfies 0.001≦z≦0.049. With the variable z satisfying 0.008≦z≦0.026, the luminous efficiency can be further increased and thus more preferable.

Preferable Combination

In the first red phosphor, a preferable combination, can be shown below.

M² is Sc or Lu and X is Cl or Br.

The variable a satisfies 0.094≦a≦0.462, M² is Sc or Lu, and X is Cl or Br.

More preferable combination in the first red phosphor can be shown below.

M¹ is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn, a satisfies 0.094≦a≦0.462; M² is Sc, b satisfies 0<b≦0.495; M⁶ is Ca, X is Cl, f satisfies 0<f≦1.472; M⁷ is Ga, g satisfies 0<g≦0.295; and z satisfies 0<z<0.1.

Second Red Phosphor

A second red phosphor can be represented by following formula (2):

(x-b)MgO.bM²O_(1.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (2)

-   -   where x, y, z, b, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597,         0<z<0.1, 0≦b≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-b), and further,         b and g satisfy b+g≠0;     -   M² is at least one element selected from the group consisting of         Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,         and Lu;     -   M⁶ is at least one element selected from the group consisting of         Mg, Ca, Sr, Ba, and Zn;     -   M⁷ is at least one element selected from the group consisting of         B, Al, Ga, and In; and     -   X is at least one element selected from the group consisting of         F, Cl, Br, and I, and     -   where M⁶X₂ is other than MgF₂.

In the second red phosphor, the variables b, f, and g satisfy 0≦b≦1.0, 0<f≦2.0, and 0≦g<0.484, and further, b and g satisfy b+g≠0. That is, the second red phosphor has a composition of a MGF phosphor in which a portion of MgF₂ is substituted by M⁶X₂, and a portion of Mg of MgO is substituted by M², and/or a portion of Ge of GeO₂ is substituted by M⁷.

In the second red phosphor, x, y, b, f, and g are, including the preferred embodiments, as those described in the first red phosphor. In the second red phosphor, the variables x and b satisfy 1.144<(x-b) and preferably satisfy 2.422≦(x-b)≦5.189. With (x-b) equal or lower than 1.144, an excessive amount of M²O_(1.5) is substituted in the MgO site, resulting in a small luminous efficiency.

Preferable Combination

In the second red phosphor, a preferable combination can be shown below.

M² is Sc or Lu and X is Cl or Br.

More preferable combinations in the second red phosphor can be shown below.

M² is Sc, b satisfies 0<b≦0.495; M⁶ is Ca, X is Cl, f satisfies 0<f≦1.472; z satisfies 0<z<0.1; and g=0, M⁶ is Ca, X is Cl, and f satisfies 0<f≦1.472; M⁷ is Ga, g satisfies 0<g≦0.295; z satisfies 0<z<0.1; and b=0.

M² is Sc and b satisfies 0<b≦0.495; M⁶ is Ca, X is Cl, and f satisfies 0<f≦1.472; M⁷ is Ga and g satisfies 0<g≦0.295; and z satisfies 0<z<0.1.

M² is Sc and b satisfies 0<b≦0.495; M⁶ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn; X is Cl or Br and f satisfies 0<f≦1.472; M⁷ is Ga, and g satisfies 0<g≦0.295; and z satisfies 0<z<0.1.

Third Red Phosphor

A third red phosphor can be represented by following formula (3):

(x-c)MgO.cM³O_(0.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (3)

-   -   where x, y, z, c, f, and g satisfy 1.144≦x≦11.0; 0<y<1.597,         0<z<0.1, 0<c≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-c);     -   M³ is at least one element selected from the group consisting of         Li, Na, and K;     -   M⁶ is at least one element selected from the group consisting of         Mg, Ca, Sr, Ba, and Zn;     -   M⁷ is at least one element selected from the group consisting of         B, AL, Ga, and In; and     -   X is at least one element selected from the group consisting of         F, Cl, Br, and I; and     -   where M⁶X₂ is other than MgF₂.

In the formula (3), the variables c, f, and g satisfy 0<c≦1.0, 0<f≦2.0, and 0≦g<0.484. That is, the third red phosphor has a composition of a MGF phosphor in which a portion of MgF₂ is substituted by M⁶X₂, and a portion of Mg of MgO is substituted by M³, and when appropriate, a portion of Ge of GeO₂ is substituted by M⁷.

cM³O_(0.5)

M³O_(0.5) is a component for substituting MgO. M³ is at least one element selected from the group consisting of Li, Na, and K, and K is preferable. The variable c satisfies 0<c≦1.0, and preferably satisfy 0<c<0.495. With the variable c satisfying 0.001≦c≦0.320, preferably satisfying 0.006≦c≦0.320, the luminous efficiency can be further increased, and thus more preferable.

In the third red phosphor, x, y, z, f, and g are, including the preferred embodiments, as those described in the first red phosphor. In the third red phosphor, the variables x and c satisfy 1.144<(x-c) and preferably satisfy 2.422≦(x-c)≦5.189. With (x-c) equal or smaller than 1.144, an excessive amount of M³O_(1.5) is substituted in the MgO site, resulting in a small luminous efficiency.

Preferable Combination

In the third red phosphor, a preferable combination can be shown below.

M³ is K and X is Cl or Br.

Fourth Red Phosphor

A fourth red phosphor can be represented by following formula (4).

(x-d)MgO.dM⁴O_(2.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (4)

-   -   where x, y, z, d, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597,         0<z<0.1, 0<d≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-d);     -   M⁴ is at least one element selected from the group consisting of         V, Nb, and Ta;     -   M⁶ is at least one element selected from, the group consisting         of Mg, Ca, Sr, Ba, and Zn;     -   M⁷ is at least one element selected from the group consisting of         B, Al, Ga, and In; and     -   X is at least one element selected from the group consisting of         F, Cl, Br, and I; and     -   where M⁶X₂ is other than MgF₂.

In the formula (4), the variables d, f, and g satisfy 0<d≦1.0, 0<f≦2.0, and 0≦g<0.484. That is, the fourth red phosphor has a composition of a MGF phosphor in which a portion of MgF₂ is substituted by M⁶X₂, a portion of Mg of MgO is substituted by M⁴, and when appropriate, a portion of Ge of GeO₂ is substituted by M⁷.

dM⁴O_(2.5)

M⁴O_(2.5) is a component for substituting MgO. M⁴ is at least one element selected from the group consisting of V, Nb, and Ta, and Ta is preferable.

The variable d satisfies 0<d≦1.0, and preferably satisfy 0<d<0.495. With the variable d satisfying 0.001≦d≦0.320, preferably satisfying 0.006≦d≦0.320, the luminous efficiency can be further increased, and thus more preferable.

In the fourth red phosphor, x, y, z, f, and g are, including the preferred embodiments, as those described in the first red phosphor.

In the fourth red phosphor, the variables x and d satisfy 1.144<(x-d) and preferably satisfy 2.422≦(x-d)≦5.189. With (x-d) equal or smaller than 1.144, an excessive amount of M⁴O_(2.5) is substituted in the MgO site, resulting in a small luminous efficiency.

Preferable Combination

In the fourth red phosphor, a preferable combination can be shown below.

M⁴ is Ta and X is Cl or Br.

Fifth Red Phosphor

A fifth red phosphor can be represented by following formula (5):

(x-e)MgO.eM⁵O₃.yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (5)

-   -   where x, y, z, e, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597,         0<z<0.1, 0<e≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-e);     -   M⁵ is at least one element selected from the group consisting of         Cr, Mo, and W;     -   M⁶ is at least one element selected from the group consisting of         Mg, Ca, Sr, Ba, and Zn:     -   M⁷ is at least one element selected from the group consisting of         B, Al, Ga, and In; and     -   X is at least one element selected from the group consisting of         F, Cl, Br, and I; and     -   where M⁶X₂ is other than MgF₂.

In the formula (5), the variables e, f, and g satisfy 0<e≦1.0, 0<f≦2.0, and 0≦g<0.484. That is, the fifth red phosphor has a composition of a MGF phosphor in which a portion of MgF₂ is substituted by M⁶X₂, a portion of Mg of MgO is substituted by M⁵, and when appropriate, a portion of Ge of GeO₂ is substituted by M⁷.

eM⁵O₃

eM⁵O₃ is a component for partially substituting MgO. M⁵ is at least one element selected from the group consisting of Cr Mo, and W and Mo is preferable. The variable e satisfies 0<e≦1.0, and preferably satisfy 0<e<0.495. Further, with the variable e satisfying 0.001≦e≦0.320, preferably satisfying 0.006≦e≦0.320, the luminous efficiency can be further increased and thus further preferable.

In the fifth red phosphor, x, y, z, f, and g are, including the preferred embodiments, as those described: in the first red phosphor.

In the fifth red phosphor, the variables x and e satisfy 1.144<(x-e) and preferably satisfy 2.422≦(x-e)≦5.189. With (x-e) equal or smaller than 1.144, an excessive amount of M⁵O₃ is substituted in the MgO site, resulting in a small luminous efficiency.

Preferable Combination

In the fifth red phosphor, a preferable combination can be shown below.

M⁵ is Mo and X is Cl or Br.

Method of Manufacturing Red Phosphor

The red phosphor can be manufactured through a method that includes mixing starting raw materials to obtain a raw material mixture, and heat treating the raw material mixture to obtain a calcined product.

Examples of the starting raw materials include an oxide, a hydroxide, a fluoride, a bromide, an iodide, a chloride, and a carbonate of elements that constitutes the red phosphor. Each of the raw starting materials is weighed based on the composition ratio of the red phosphor to obtain. The mixing can be carried out by using a known mixing device. Examples of such a known mixing device include a high-speed shear-type mixer, a ball mill, a V-type mixer, and a stirring blender.

The mixed raw material is charged in a calcining vessel such as a crucible and heat-treated to obtain a calcined product. The heat treatment can be performed in an air atmosphere, an N₂ atmosphere, or an Ar atmosphere, and an air atmosphere is preferable.

The temperature of the heat treatment can be set appropriately and which is preferably in a range of 1000° C. to 1400° C., and more preferably in a range of 1000° C. to 1300° C. The heat treatment at a temperature of 1000° C. or greater can accelerate the reaction of the raw materials. Also, the heat treatment at a temperature of 1400° C. or lower can reduce possibilities of fluctuation in the composition due to melting of the raw material or the calcined product or to volatilization of a portion of the raw materials.

The length of the heat treatment can be in a range of 0.5 to 20 hours, and preferably in a range of 4 to 12 hours. The reaction of the raw materials can be accelerated with the heat treatment of 0.5 hours or longer. Meanwhile, the heat treatment of 20 hours or less can reduce the possibilities of fluctuation in the composition due to melting of the raw material or the calcined product or to volatilization of a portion of the raw materials.

Accordingly, the red phosphor can be obtained. The amount of each element of the red phosphor substantially corresponds to the charging ratio of its raw material.

EXAMPLES

The examples below illustrate certain embodiments of the present disclosure in detail. However, the embodiments are not limited to those illustrated below.

Examples 1-20 and 27-45 each illustrates a second red phosphor. Examples 21-26 each illustrates a first red phosphor. Example 46 illustrates a third red phosphor. Example 47 illustrates a fourth red phosphor. Example 48 illustrates a fifth red phosphor.

Examples 1-13, Comparative Examples 2,3

For the raw materials, MgO, MgF₂, CaCl₂, GeO₂, MnCO₃ were exactly weighed. Then, for the raw materials of the elements for substituting MgO or GeO₂, SC₂O₃ and Ga₂O₃ were exactly weighed. Then, the weighed raw materials were mixed by using a rotation blade type mixing machine. The mixed raw material was calcined in an air atmosphere at a temperature in a range of 1000 to 1300° C., for 4 to 12 hours. Thus, the red phosphors according to Examples 1-13 and Comparative Examples 2 and 3, whose composition formulas are shown in Table 1 were obtained.

Comparative Example 1

A MGF phosphor of Comparative Example, represented by a composition formula 3.5MgO.0.5MgF₂.GeO₂0.015Mn⁴⁺ was prepared using the raw materials and calcining conditions as in the Example described above. The MGF phosphor thus obtained was used as the phosphor of Comparative Example 1.

TABLE 1 Substituting Element Composition Formula Example 1 Sc, CaCl₂ 3.095MgO•0.0025Sc₂O₃•0.65MgF₂•0.25CaCl₂•GeO₂:0.015Mn⁴⁺ Example 2 Sc, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•GeO₂:0.015Mn⁴⁺ Example 3 Sc, CaCl₂ 3.0MgO•0.05Sc₂O₃•0.65MgF₂•0.25CaCl₂•GeO₂:0.015Mn⁴⁺ Example 4 Sc, CaCl₂ 2.8MgO•0.15Sc₂O₃•0.65MgF₂•0.25CaCl₂•GeO₂:0.015Mn⁴⁺ Example 5 Sc, CaCl₂ 2.6MgO•0.25Sc₂O₃•0.65MgF₂•0.25CaCl₂•GeO₂:0.015Mn⁴⁺ Example 6 Ga, CaCl₂ 3.1MgO•0.65MgF₂•0.25CaCl₂•0.995GeO₂•0.0025Ga₂O₃:0.015Mn⁴⁺ Example 7 Ga, CaCl₂ 3.1MgO•0.65MgF₂•0.25CaCl₃•0.95GeO2•0.025Ga₂O₃:0.015Mn⁴⁺ Example 8 Ga, CaCl₂ 3.1MgO•0.65MgF₂•0.25CaCl₂•0.90GeO₂•0.05Ga₂O₃:0.015Mn⁴⁺ Example 9 Ga, CaCl₂ 3.1MgO•0.65MgF₂•0.25CaCl₂•0.70GeO₂•0.15Ga₂O₃:0.015Mn⁴⁺ Comparative Ga, CaCl₂ 3.1MgO•0.65MgF₂•0.25CaCl₂•0.50GeO₂•0.25Ga₂O₃:0.015Mn⁴⁺ Example 2 Example 10 Sc, Ga, CaCl₂ 3.095MgO•0.0025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.995GeO₂•0.0025Ga₂O₃:0.015Mn⁴⁺ Example 11 Sc, Ga, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 12 Sc, Ga, CaCl₂ 3.0MgO•0.05Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.90GeO₂•0.05Ga₂O₃:0.015Mn⁴⁺ Example 13 Sc, Ga, CaCl₂ 2.8MgO•0.15Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.70GeO₂•0.15Ga₂O₃:0.015Mn⁴⁺ Comparative Sc, Ga, CaCl₂ 2.6MgO•0.25Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.50GeO₂•0.25Ga₂O₃:0.015Mn⁴⁺ Example 3 Comparative — 3.5MgO•0.5MgF₂•0.985GeO₂:0.015Mn⁴⁺ Example 1

Measuring Emission Spectra

The emission spectra excited by light of an excitation wavelength in a range of 350 to 500 nm were measured for the red phosphors obtained in Example 12, the MGF phosphor (composition formula: 3.5MgO.0.5MgF₂.GeO_(2:)0.15Mn⁴⁺) of Comparative Example 1. and the CASN phosphor (composition formula: CaAlSiN₃:Eu²⁺) of Reference Example were measured. The results are shown in FIG. 1. As shown in FIG. 1, the red phosphor obtained in Example 12 was excited by light having a wavelength in a range of 350 to 500 nm and emitted light having a wavelength in a wavelength region of 600 to 670 nm. Further, the red phosphor of Example 12 emitted light having a half value width of the emission spectrum smaller than the CASN phosphor shown as a reference example.

Measuring Excitation Spectra

Excitation spectra of the red phosphors obtained in Examples 3, 8, and 12 and the MGF phosphor of Comparative Example 1 were measured at wavelengths of 220-570 nm. The results are shown in FIG, 2, The red phosphor of Example 3 is obtained by substituting a portion of MgF₂ by CaCl₂ and substituting a portion of Mg of MgO by Sc (hereinafter may be referred to as “Sc-substituted”). The red phosphor of Example 8 is obtained by substituting a portion of MgF₂ by CaCl₂ and substituting a portion of GeO₂ by GaO_(1.5) (hereinafter may be referred to as “Ga-substituted”). The red phosphor of Example 12 is obtained by substituting a portion of MgF₂ by CaCl₂, substituting a portion of MgO by ScO_(1.5), and substituting a portion of GeO₂ by GaO_(1.5) (hereinafter may be referred to as “Ga—Sc co-substituted”). As shown in FIG. 2, the red phosphors of Examples 3, 8, and 12 exhibited higher relative intensities when excited by the near-ultraviolet light or blue light of wavelengths of 350-500 nm. Particularly, the phosphor of Example 12 is Ga—Se co-substituted and exhibited a higher relative intensity when excited by the near-ultraviolet light or blue light of wavelengths of 350-500 nm, compared to that of the phosphor of Example 3. which is Sc-substituted, and the phosphor of Example 5, which is Ge-substituted.

Measuring Luminance of Phosphor Powder

Luminance of the powder of the red phosphors of Examples 1-13 and Comparative Examples 2 and 3 were measured at an excitation wavelength of 440 nm, by using a fluorescence spectrophotometer F-4500 (Hitachi High-Technologies Corporation). Relative energy value (relative ENG) of the emission spectrum of each phosphor of examples and comparative examples at an excitation wavelength of 440 nm was determined with an energy value of emission spectrum of the phosphor of Comparative Example 1 (MGF phosphor) set to 100%. The results are shown in Table 3. The energy values are represented in relative integral values in a wavelength range of 460 to 830 nm in the emission spectra, respectively.

Composition of Phosphors

The compositions of the red phosphors of Examples 1-13 and Comparative Examples 2, 3 were analyzed by using an inductive coupling plasma emission analysis (ICP analysis) and a spectrophotometer. The results are shown in Table 3.

TABLE 2 Charging Ratio Molar Ratio (mol) Mg-Site Ge-Site MgO M²O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ x − b M² b y M⁶ X f 1 − g M⁷ g z Comparative 3.5 — — 0.5 — — — 1.0 — — 0.015 Example 1 Example 1 3.095 Sc 0.005 0.65 Ca Cl 0.25 1.0 — — 0.015 Example 2 3.05 0.05 Example 3 3.00 0.10 Example 4 2.80 0.30 Example 5 2.60 0.50 Example 6 3.10 — — 0.995 Ga 0.005 Example 7 0.95 0.05 Example 8 0.90 0.10 Example 9 0.70 0.30 Comparative 0.50 0.50 Example 2 Example 10 3.095 Sc 0.005 0.995 0.005 Example 11 3.05 0.05 0.95 0.05 Example 12 3.00 0.10 0.90 0.10 Example 13 2.80 0.30 0.70 0.30 Comparative 2.60 0.50 0.50 0.50 Example 3

TABLE 3 Analytical Value Powder Molar Ratio (mol) Characteristics Mg-Site Ge-Site 440 nm Rela- MgO M²O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ tive ENG x − b M² b y M⁶ X f 1 − g M⁷ g z (%) Comparative 3.473 — — 0.286 — — — 1.000 — — 0.015 100 Example 1 Example 1 3.446 Sc 0.007 0.488 Ca Cl 0.397 1.000 — — 0.013 172 Example 2 3.503 0.049 0.488 0.367 1.000 0.013 190 Example 3 3.410 0.110 0.467 0.366 1.000 0.013 182 Example 4 3.178 0.320 0.496 0.380 1.000 0.013 154 Example 5 2.906 0.495 0.458 0.333 1.000 0.013 132 Example 6 3.385 — — 0.517 0.360 0.997 Ga 0.003 0.013 146 Example 7 3.385 0.572 0.359 0.965 0.035 0.014 141 Example 8 3.413 0.569 0.363 0.915 0.085 0.014 153 Example 9 3.467 0.576 0.360 0.730 0.270 0.013 129 Comparative 3.477 0.518 0.356 0.516 0.484 0.013 75 Example 2 Example 10 3.318 Sc 0.006 0.517 0.350 0.982 0.018 0.013 168 Example 11 3.497 0.050 0.532 0.259 0.950 0.050 0.015 201 Example 12 3.328 0.099 0.451 0.341 0.907 0.093 0.013 213 Example 13 3.088 0.296 0.470 0.337 0.705 0.295 0.013 148 Comparative 2.954 0.493 0.504 0.334 0.504 0.496 0.013 53 Example 3

The red phosphors of Examples 1-5 are Sc-substituted phosphors. Accordingly, a larger relative energy was exhibited in each red phosphor. Particularly, a very large relative energy was exhibited in each of the red phosphors of Examples 1 to 4, in which a substitution amount of Sc was in a range of 0.007 to 0.320 mol (b satisfies 0.007≦b≦0.320).

The red phosphors of Examples 6-9 are Ge-substituted phosphors. Accordingly, a larger relative energy was exhibited in each red phosphor. However, in the case of Ge-substitution, the red phosphor of Comparative Example 2 in which the substitution amount of Ga was 0.484 mol (g=0.484) resulted in a significantly small relative ENG.

The red phosphors of Examples 10-13 are Ga—Sc co-substituted phosphors. Particularly, a relative energy that exceeding 200% was exhibited in the,red phosphors of Examples 11 and 12, in which in the Ga—Sc co-substitution, a substitution amount of Sc in a range of 0.050 to 0.099 mol (b satisfies 0.050≦b≦0.099), and a substitution amount of Ga in a range of 0.050 to 0.093 mol (g satisfies 0.050≦g≦0.093). However, in the case of Ga—Sc co-substitution, the red phosphor of Comparative Example 3 in which the substitution amount of Ga was 0.496 mol (g=0.496) exhibited a very small relative energy.

FIG. 3 is a diagram showing relative energies excited at 440 nm of Sc-substituted phosphors of Examples 2 to 6, Ge-substituted phosphors of Examples 6 to 9 and Comparative Example 2, the Ga—Sc co-substituted phosphors of Examples 10 to 13 and Comparative Example 3, each corresponding to respective substituting amounts (mol).

As shown in FIG. 3, the phosphors of Examples 11 and 12 in which the substitution amount of Sc is in a range of 0.050 to 0.099 mol (b satisfies 0.050≦b≦0.099) and the substitution amount of Ga is in a range of 0.050 to 0.093 mol (g satisfies 0.050≦g≦0.093) exhibited larger relative energies compared to that of the phosphors of Examples 2 and 3 with an approximately same substitution amount of Sc and to that of the phosphors of Examples 7 and 8 with Ga. This is thought that simultaneously substituting elements of different valence numbers with a specific amount allows for further increase in the effect of charge compensation, which can further suppress concentration quenching. However, the phosphor of Comparative Example 3 has an excessive substitution amount of Ga, which resulting in a very small relative ENG.

Examples 14-20, Comparative Examples 4-6

For the raw materials, MgO, MgF₂, CaCl₂, GeO₂, MnCO₃ were exactly weighed. Then, for the raw materials of the elements for substituting MgO or GeO₂, Sc₂O₃ and Ga₂O₃ were exactly weighed. Then, the weighed raw materials were mixed by using a rotation blade type mixing machine. The mixed raw material was calcined in an air atmosphere at a temperature in a range of 1000 to 1300° C; for 4 to 12 hours. Thus, the red phosphors according to Examples 14 to 20 and Comparative Examples 4 to 6, whose composition formulas are shown in Table 4 were obtained. The luminance of phosphor powder and the composition of the red phosphors of Examples 14 to 20 and Comparative Examples 4 to 6 were measured in a similar manner as in Example 1. The charging ratios for the phosphors are shown in Table 5 below. The relative energies and the compositions of the phosphors are shown in Table 6 below.

TABLE 4 Substituting Element Composition Formula Comparative Sc, Ga, CaCl₂ 1.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 4 Example 14 Sc, Ga, CaCl₂ 2.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 15 Sc, Ga, CaCl₂ 5.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 16 Sc, Ga, CaCl₂ 10.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Comparative Sc, Ga, CaCl₂ 3.7MgO•0.025Sc₂O₃•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 5 Example 17 Sc, Ga, CaCl₂ 3.6MgO•0.025Sc₂O₃•0.1MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 18 Sc, Ga, CaCl₂ 3.45MgO•0.025Sc₂O₃•0.25MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 19 Sc, Ga, CaCl₂ 2.45MgO•0.025Sc₂O₃•1.25MgF₅•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 20 Sc, Ga, CaCl₂ 2.2MgO•0.025Sc₂O₃•1.5MgF₅•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Comparative Sc, Ga, CaCl₂ 2.7MgO•0.025Sc₂O₃•2.0MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 6 Comparative — 3.5MgO•0.5MgF₂•GeO₂:0.015Mn⁴⁺ Example 1

TABLE 5 Charging Ratio Molar Ratio (mol) Mg-Site Ge-Site MgO M²O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ x − b M² b y M⁶ X f 1 − g M⁷ g z Comparative 3.5 — — 0.5 — — — 1.0 — — 0.015 Example 1 Comparative 1.05 Sc 0.05 0.65 Ca Cl 0.25 0.95 Ga 0.05 0.015 Example 4 Example 14 2.05 Example 15 5.05 Example 16 10.05 Comparative 3.7 0 Example 5 Example 17 3.6 0.1 Example 18 3.45 0.25 Example 19 2.45 1.25 Example 20 2.2 1.5 Comparative 1.7 2.0 Example 6

TABLE 6 Analytical Value Powder Molar Ratio (mol) Characteristics Mg-Site Ge-Site 440 nm Rela- MgO M²O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ tive ENG x − b M² b y M⁶ X f 1 − g M⁷ g z (%) Comparative 3.473 — — 0.286 — — — 1.000 — — 0.015 100 Example 1 Comparative 1.144 Sc 0.049 0.674 Ca Cl 0.255 0.976 Ga 0.024 0.009 43 Example 4 Example 14 2.422 0.051 0.403 0.335 0.953 0.047 0.014 177 Example 15 5.189 0.049 0.470 0.348 0.953 0.047 0.015 177 Example 16 10.039 0.048 0.530 0.164 0.957 0.043 0.012 132 Comparative 3.963 0.049 0.000 0.371 0.953 0.047 0.012 2 Example 5 Example 17 4.069 0.054 0.160 0.327 0.950 0.050 0.015 127 Example 18 3.672 0.050 0.241 0.369 0.951 0.049 0.015 151 Example 19 2.925 0.049 0.856 0.305 0.953 0.047 0.015 205 Example 20 2.469 0.048 1.213 0.288 0.959 0.041 0.014 164 Comparative 2.107 0.049 1.597 0.222 0.959 0.041 0.011 86 Example 6

The red phosphors of Examples 14 to 16 have different content of MgO but otherwise approximately same composition ratio. Even a large amount of MgO is contained in the red phosphors, the relative ENG changes little, but the phosphors of Examples 14 and 15 with a content of MgO m a range of 2.422 to 5.189 mol (x-b satisfies 2,422≦(x-b)≦5.189) exhibited larger relative ENG. However, the phosphor of Comparative Example 4 having a MgO content of 1.144 mol ((x-b)=1.144) exhibited a significantly small relative ENG. The red phosphors of Examples 17 to 20 and Comparative Examples 5 and 6 have different content of MgO and MgF₂ but otherwise approximately same composition ratio. The red phosphor of Comparative Example 5 does not contain MgF₂ (y=0), so that exhibited very small relative ENG. In the phosphors of Examples 17 to 20, the larger content of MgF₂, the larger the relative ENG. However, the phosphor of Comparative Example 6 in which the content of MgF₂ was 1.597 mol (y=1.597) exhibited a very small relative ENG.

Examples 21-26, Comparative Example 7

For the raw materials, MgO, MgF₂, CaCl₂, GeO₂, MnCO₃ were exactly weighed. Then, for the raw materials of the elements for substituting MgO or GeO₂, CaCO₃, SrCO₃, BaCO₃, ZnO, Sc₂O₃ and Ga₂O₃ were exactly weighed. Then, the weighed raw materials were mixed by using a rotation blade type mixing machine. The mixed raw material was calcined in an air atmosphere at a temperature in a range of 1000 to 1300° C., for 4 to 12 hours. Thus, the red phosphors according to Examples 21 to 26 and Comparative Example 7, whose composition formulas are shown in Table 7 were obtained. The luminance of phosphor powder and the composition of the red phosphors of Examples 21 to 26 and Comparative Example 7 were measured in a similar manner as in Example 1. The charging ratios for the phosphors are shown in Table 8 below. The relative energies and the compositions of the phosphors are shown in Table 9 below.

TABLE 7 Substituting Element Composition Formula Example 21 CaO, Sc, Ga, CaCl₂ 2.95MgO•0.1CaO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 22 CaO, Sc, Ga, CaCl₂ 2.85MgO•0.2CaO•0.025Sc₂O₃•0.65MgF₃•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 23 CaO, Sc, Ga, CaCl₂ 2.55MgO•0.5CaO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Comparative CaO, Sc, Ga, CaCl₂ 2.05MgO•0.1CaO•0.025Sc₂O₃•0.65MgF₃•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 7 Example 24 SrO, Sc, Ga, CaCl₂ 2.75MgO•0.3SrO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 25 BaO, Sc, Ga, CaCl₂ 2.75MgO•0.3BaO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 26 ZnO, Sc, Ga, CaCl₂ 2.75MgO•0.3ZnO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Comparative — 3.5MgO•0.5MgF₂•GeO₂:0.015Mn⁴⁺ Example 1

TABLE 8 Charging Ratio Molar Ratio (mol) Mg-Site Ge-Site MgO M¹O M²O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ x − a − b M¹ a M² b y M⁶ X f 1 − g M⁷ g z Comparative 3.5 — — — — 0.5 — — — 1.0 — — 0.015 Example 1 Example 21 2.95 Ca 0.1 Sc 0.05 0.65 Ca Cl 0.25 0.95 Ga 0.05 0.015 Example 22 2.85 0.2 Example 23 2.55 0.5 Comparative 2.05 1.0 Example 7 Example 24 2.75 Sr 0.3 Example 25 Ba Example 26 Zn

TABLE 9 Analytical Value Powder Molar Ratio (mol) Characteristics Mg-Site Ge-Site 440 nm Rela- MgO M¹O M²O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ tive ENG x − a − b M¹ a M² b y M⁶ X f 1 − g M⁷ g z (%) Comparative 3.473 Ca — — — 0.286 — — — 1.000 — — 0.015 100 Example 1 Example 21 3.289 0.382 Sc 0.048 0.556 Ca Cl 0.002 0.952 Ga 0.048 0.014 183 Example 22 3.235 0.462 0.051 0.558 0.009 0.951 0.049 0.014 208 Example 23 3.069 0.419 0.049 0.431 0.038 0.951 0.049 0.015 173 Comparative 2.423 1.083 0.050 0.627 0.091 0.951 0.049 0.015 65 Example 7 Example 24 3.163 Sr 0.248 0.051 0.463 0.248 0.951 0.049 0.015 204 Example 25 3.209 Ba 0.254 0.050 0.468 0.283 0.950 0.050 0.014 162 Example 26 3.002 Ba 0.094 0.051 0.444 0.194 0.950 0.050 0.014 213

The red phosphors of Examples 21-23, and Comparative Example 7 each has a composition of the first red phosphor in which the contents of GaO that substitutes a portion of MgO are different. The red phosphor of Comparative Example 7 in which the content of CaO was 1.083 mol (a=1.083) exhibited a very small relative energy.

Further, as shown in Examples 24-26, the red phosphors in which CaO for substituting a portion of MgO was replaced by SrO, BaO, or ZnO exhibited similar relative energies as of the red phosphors of Examples 21-23.

Examples 27-36

For the raw materials, MgO, MgF₂, CaCl₂, GeO₂, MnCO₃ were exactly weighed. Then, for the raw materials of the elements for substituting MgO, GeO₂, or MgF₂, Sc₂O₃, Ga₂O₃, CaF₂, MgCl₂.6H₂O, SrCl₂, BaCl₂, ZnCl₂, MgBr₂,6H₂O, and CaBr₂ were exactly weighed. Then, the weighed raw materials were mixed by using a rotation blade type mixing machine. The raw material mixture was calcined in an air atmosphere at a temperature in a range of 1000 to 1300° C. for 4 to 12 hours. Thus, the red phosphors of Examples 27-36 whose composition formulas are shown in Table 10 were obtained. The luminance of phosphor powder and the composition of the red phosphors of Examples 27-36 were measured in a similar manner as in Example 1. The charging ratios for the phosphors are shown in Table 11 below. The relative energies and the compositions of the phosphors are shown in Table 12 below.

TABLE 10 Substituting Element Composition Formula Example 27 Sc, Ga, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.7MgF₂•0.2CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 28 Sc, Ga, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₂•0.5CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 29 Sc, Ga, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₂•1.0CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 30 Sc, Ga, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₂•1.5CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 31 Sc, Ga, MgCl₂ 3.05MgO•0.025Sc₂O₃•0.7MgF₂•0.2MgCl₂•0.95GeO₃•0.025Ga₂O₃:0.015Mn⁴⁺ Example 32 Sc, Ga, SrCl₂ 3.05MgO•0.025Sc₂O₃•0.7MgF₂•0.2SrCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 33 Sc, Ga, BaCl₂ 3.05MgO•0.025Sc₂O₃•0.7MgF₂•0.2BaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 34 Sc, Ga, ZnCl₂ 3.05MgO•0.025Sc₂O₃•0.7MgF₂•0.2ZnCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 35 Sc, Ga, MgBr₂ 3.05MgO•0.025Sc₂O₃•0.7MgF₂•0.2MgBr₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Example 36 Sc, Ga, CaBr₂ 3.05MgO•0.025Sc₂O₃•0.7MgF₂•0.2CaBr₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Comparative — 3.5MgO•0.5MgF₂•GeO₂•:0.015Mn⁴⁺ Example 1

TABLE 11 Charging Ratio Molar Ratio (mol) Mg-Site Ge-Site MgO M²O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ x − b M² b y M⁶ X f 1 − g M⁷ g z Comparative 3.5 — — 0.5 — — — 1.0 — — 0.015 Example 1 Example 27 3.05 Sc 0.05 0.7 Ca Cl 0.2 0.95 Ga 0.05 0.015 Example 28 0.65 0.5 Example 29 1.0 Example 30 1.5 Example 31 0.7 Mg Cl 0.2 Example 32 Sr Example 33 Ba Example 34 Zn Example 35 Mg Br Example 36 Ca

TABLE 12 Analytical Value Powder Molar Ratio (mol) Characteristics Mg-Site Ge-Site 440 nm Rela- MgO M²O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ tive ENG x − b M² b y M⁶ X f 1 − g M⁷ g z (%) Comparative 3.473 — — 0.286 — — — 1.000 — — 0.015 100 Example 1 Example 27 3.312 Sc 0.051 0.660 Ca Cl 0.296 0.953 Ga 0.047 0.015 190 Example 28 3.293 0.050 0.564 0.463 0.953 0.047 0.014 204 Example 29 3.468 0.050 0.469 0.852 0.955 0.045 0.013 202 Example 30 3.271 0.050 0.630 1.472 0.957 0.043 0.013 144 Example 31 3.747 0.050 0.456 Mg Cl 0.002 0.949 0.051 0.014 137 Example 32 3.397 0.049 0.563 Sr 0.185 0.952 0.048 0.014 194 Example 33 3.457 0.049 0.488 Ba 0.210 0.951 0.049 0.014 161 Example 34 3.816 0.053 0.343 Zn 0.054 0.947 0.053 0.012 172 Example 35 3.961 0.054 0.360 Mg Br 0.0002 0.947 0.053 0.013 152 Example 36 3.589 0.052 0.477 Ca 0.185 0.949 0.051 0.012 188

As shown in Table 12, the red phosphors of Examples 27 to 30 each has a composition of the Ga—Sc co-substituted second red phosphor in which the ratios of MgF₂ and CaCl₂ are changed hut the composition ratios of others are approximately fixed. The red phosphors of Examples 28 and 29 each contains specific amounts of MgF₂ and CaCl₂ exhibit the relative energies exceeding 200%. Further, as shown in Examples 31 to 36, the red phosphors in which CaCl₂ that substitutes a portion of MgF₂ is changed to MgCl₂, SrCl₂, BaCl₂, ZnCl₂, MgBr₂, or CaBr₂ exhibit the relative energies similar to the relative energy of the red phosphor of Example 27.

Examples 37-40, Comparative Example 8

For the raw materials, MgO, MgF₂, CaCl₂, GeO₂, MnCO₃ were exactly weighed. Then, for the raw materials of the elements for substituting MgO or GeO₂, Sc₂O₃ and Ga₂O₃ were exactly weighed. Then, the weighed raw materials were mixed by using a rotation blade type mixing machine. The mixture of the raw materials was calcined in an air atmosphere at a temperature in a range of 1000 to 1300 for 4 to 12 hours. Thus, the red phosphors of Examples 37 to 40 and Comparative Example 8, whose composition formulas are shown in Table 13 were obtained. The luminance of phosphor powder and the composition of the red phosphors of Examples 37 to 40 and Comparative Example 8 were measured in a similar manner as in Example 1. The charging ratios for the phosphors are shown in Table 14 below. The relative energies and the compositions of the phosphors are shown in Table 15 below.

TABLE 13 Substituting Element Composition Formula Example 37 Sc, Ga, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.001Mn⁴⁺ Example 38 Sc, Ga, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.01Mn⁴⁺ Example 39 Sc, Ga, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.03Mn⁴⁺ Example 40 Sc, Ga, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.05Mn⁴⁺ Comparative Sc, Ga, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₃•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.1Mn⁴⁺ Example 8 Comparative — 3.5MgO•0.5MgF₂•GeO₂:0.015Mn⁴⁺ Example 1

TABLE 14 Charging Ratio Molar Ratio (mol) Mg-Site Ge-Site MgO M²O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ x − b M² b y M⁶ X f 1 − g M⁷ g z Comparative 3.5 — — 0.5 — — — 1.0 — — 0.015 Example 1 Example 37 3.05 Sc 0.05 0.65 Ca Cl 0.25 0.95 Ga 0.05 0.001 Example 38 0.01 Example 39 0.03 Example 40 0.05 Comparative 0.1 Example 8

TABLE 15 Analytical Value Powder Molar Ratio (mol) Characteristics Mg-Site Ge-Site 440 nm Rela- MgO M₂O_(1.5) MgF₂ M⁶X₂ GeO₂ M₇O_(1.5) Mn⁴⁺ tive ENG x − b M² b y M⁶ X f 1 − g M⁷ g z (%) Comparative 3.473 — — 0.286 — — — 1.000 — — 0.015 100 Example 1 Example 37 3.363 Sc 0.050 0.644 Ca Cl 0.290 0.953 Ga 0.047 0.001 132 Example 38 3.348 0.049 0.500 0.338 0.954 0.046 0.008 178 Example 39 3.376 0.050 0.568 0.360 0.954 0.046 0.026 197 Example 40 3.497 0.052 0.557 0.372 0.951 0.049 0.049 120 Comparative 3.619 0.061 0.681 0.358 0.945 0.055 0.101 15 Example 8

The red phosphors of Examples 37 to 40 and Comparative Example 8 each has a composition of the Ga—Sc co-substituted second red phosphor in which the content of Mn⁴⁺ is different but the composition ratios of others are approximately fixed. As shown in Table 15, the larger the content of Mn⁴⁺ in the red phosphor, the larger the relative energy. Particularly, the red phosphors of Example 38 and 39 that have the Mn⁴⁺ contents of 0.008 to 0.026 mol (z satisfies 0.008≦z≦0.026) exhibited further higher relative energies. However, the red phosphor of Comparative Example 8 that has the Mn⁴⁺ content of 0.101 mol (z=0.101) exhibited a very small relative energy by the influence regarded as the concentration quenching.

Examples 41 to 48

For the raw materials, MgO, MgF₂, CaCl₂, GeO₂, MnCO₃ were exactly weighed. Then, for the raw material of the elements to substitute MgO, Sc₂O₃, K₂CO₃, Lu₂O₃, Ta₂O₅, or MoO₃ was exactly weighed, and for the raw material of the elements to substitute GeO₂, Ga₂O₃, H₃BO₃, In₂O₃, TiO₂, SnO₂ or Al₂O₃ was exactly weighed Then, the weighed raw materials were mixed by using a rotation blade type mixing machine. The mixture of the raw materials was calcined in an air atmosphere at a temperature in a range of 1000 to 1300° C. for 4 to 12 hours. Thus, the red phosphors of Examples 41 to 48 were obtained, The luminance of phosphor powder and the composition of the red phosphors of Examples 41 to 48 were measured in a similar manner as in Example 1. The charging ratios for the phosphors are shown in Tables 17, 19, 21, and 23 below. The relative energies and the compositions of the phosphors are shown in Tables 18, 20, 22, and 24 below.

TABLE 16 Substituting Element Composition Formula Example 41 B, CaCl₂ 3.1MgO•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ba₂O₃:0.015Mn⁴⁺ Example 42 In, CaCl₂ 3.1MgO•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025IN₂O₃:0.015Mn⁴⁺ Example 43 Sc, B, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ba₂O₃:0.015Mn⁴⁺ Example 44 Sc, Al, CaCl₂ 3.05MgO•0.025Sc₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Al₂O₃:0.015Mn⁴⁺ Example 45 Lu, B, CaCl₂ 3.05MgO•0.025Lu₂O₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ba₂O₃:0.015Mn⁴⁺ Example 46 K, B, CaCl₂ 3.05MgO•0.025K₂O₃•0.65MgF₃•0.25CaCl₂•0.95GeO₂•0.025B₂O₃:0.015Mn⁴⁺ Example 47 Ta CaCl₂ 3.05MgO•0.025Ta₂O₃•0.65MgF₂•0.25CaCl₂•GeO₂:0.015Mn⁴⁺ Example 48 Mo, Ga, CaCl₂ 3.05MgO•0.05MoO₃•0.65MgF₂•0.25CaCl₂•0.95GeO₂•0.025Ga₂O₃:0.015Mn⁴⁺ Comparative — 3.5MgO•0.5MgF₂•GeO₂:0.015Mn⁴⁺ Example 1

TABLE 17 Charging Ratio Molar Ratio (mol) Mg-Site Ge-Site MgO M²O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ x − b M² b y M⁶ X f 1 − g M⁷ g z Comparative 3.5 — — 0.5 — — — 1.0 — — 0.015 Example 1 Example 41 3.1 — — 0.65 Ca Cl 0.25 0.95 B 0.05 0.015 Example 42 In Example 43 3.05 Sc 0.05 B Example 44 Al Example 45 Lu B

TABLE 18 Analytical Value Powder Molar Ratio (mol) Characteristics Mg-Site Ge-Site 440 nm Rela- MgO M²O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ tive ENG x − b M² b y M⁶ X f 1 − g M⁷ g z (%) Comparative 3.473 — — 0.286 — — — 1.000 — — 0.015 100 Example 1 Example 41 3.338 — — 0.525 Ca Cl 0.349 0.944 B 0.056 0.014 147 Example 42 3.609 0.533 0.369 0.999 In 0.001 0.016 155 Example 43 3.334 Sc 0.048 0.499 0.324 0.949 B 0.051 0.015 193 Example 44 3.336 0.049 0.502 0.350 0.954 Al 0.046 0.012 193 Example 45 3.335 Lu 0.050 0.471 0.357 0.948 B 0.052 0.013 149

TABLE 19 Charging Ratio Molar Ratio (mol) Mg-Site Ge-Site MgO M³O_(1.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ x − c M³ c y M⁶ X f 1 − g M⁷ g z Comparative 3.5 — — 0.5 — — — 1.0 — — 0.015 Example 1 Example 46 3.05 K 0.05 0.65 Ca Cl 0.25 0.95 B 0.05 0.015

TABLE 20 Analytical Value Powder Molar Ratio (mol) Characteristics Mg-Site Ge-Site 440 nm Rela- MgO M³O_(0.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ tive ENG x − c M³ c y M⁶ X f 1 − g M⁷ g z (%) Comparative 3.473 — — 0.286 — — — 1.000 — — 0.015 100 Example 1 Example 46 3.308 K 0.001 0.521 Ca Cl 0.373 0.954 B 0.046 0.011 154

TABLE 21 Charging Ratio Molar Ratio (mol) Mg-Site Ge-Site MgO M⁴O_(2.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ x − d M⁴ d y M⁶ X f 1 − g M⁷ g z Comparative 3.5 — — 0.5 — — — 1.0 — — 0.015 Example 1 Example 47 3.05 Ta 0.05 0.65 Ca Cl 0.25 1.0 — — 0.015

TABLE 22 Analytical Value Powder Molar Ratio (mol) Characteristics Mg-Site Ge-Site 440 nm Rela- MgO M⁴O_(2.5) MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ tive ENG x − d M⁴ d y M⁶ X f 1 − g M⁷ g z (%) Comparative 3.473 — — 0.286 — — — 1.000 — — 0.015 100 Example 1 Example 47 3.336 Ta 0.046 0.456 Ca Cl 0.359 1.000 — — 0.011 157

TABLE 23 Charging Ratio Molar Ratio (mol) Mg-Site Ge-Site MgO M⁵O₃ MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ x − e M⁵ e y M⁶ X f 1 − g M⁷ g z Comparative 3.5 — — 0.5 — — — 1.0 — — 0.015 Example 1 Example 48 3.05 Mo 0.05 0.65 Ca Cl 0.25 0.95 Ga 0.05 0.015

TABLE 24 Analytical Value Powder Molar Ratio (mol) Characteristics Mg-Site Ge-Site 440 nm Rela- MgO M⁵O₃ MgF₂ M⁶X₂ GeO₂ M⁷O_(1.5) Mn⁴⁺ tive ENG x − e M⁵ e y M⁶ X f 1 − g M⁷ g z (%) Comparative 3.473 — — 0.286 — — — 1.000 — — 0.015 100 Example 1 Example 48 3.237 Mo 0.053 0.544 Ca Cl 0.358 0.957 Ga 0.043 0.011 148

As shown in Examples 41 to 45 in Table 18, the red phosphors that have compositions of the second red phosphor in which a portion of MgF₂, is substituted by CaCl₂ and a portion of Mg of MgO is substituted by Lu; and a portion of Ge of GeO₂ is substituted by B, In, or Al, respectively exhibited relative energies similar to that of the second red phosphors of Examples 2, 7, and 11 in which a portion of MgF₂ is substituted by CaCl₂, and a portion of Mg of MgO is substituted by Sc, and/or a portion of Ge of GeO₂ is substituted by Ga.

As shown in Example 46 in Table 20, the third red phosphor that has a composition of a MGF phosphor in which a portion of MgF₂ is substituted by CaCl₂, a portion of Mg of MgO is substituted by K, and a portion of Ge of GeO₂ is substituted by B, has a high luminous efficiency. Also, the luminous efficiency of the red phosphor of Example 46 was improved similar to that attained in the red phosphor of Example 11, in which K and B in the red phosphor of Example 46 are Sc and Ga.

As shown in Example 47 in Table 22, the fourth red phosphor that has a composition of a MGF phosphor, in which a portion of MgF₂ is substituted by CaCl₂ and a portion of Mg of MgO is substituted by Ta, has a high luminous efficiency. Also, the luminous efficiency of the red phosphor of Example 47 was improved similar to that attained in the second red phosphor of Example 2, in which substitution amount of Sc is approximately same as the substitution amount of Ta in the red phosphor of Example 47.

As shown in Example 48 in Table 24, the fifth red phosphor that has a composition of a MGF phosphor in which a portion of MgF₂ is substituted by CaCl₂ and a portion of Mg of MgO is substituted by Mo, has a high luminous efficiency. Also, the luminous efficiency of the red phosphor of Example 48 was improved similar to that attained in the second red phosphor of Example 11, in which substitution amounts of Sc and Ga are approximately same as the substitution amounts of Mo and Ga in the red phosphor of Example 48.

The red phosphor according to one embodiment of the present disclosure can be used in combination with a lamp to emit ultraviolet light or a light emitting diode to emit near-ultraviolet light or visible light, in a light emitting device that can emit red light with a high efficiency, or in combination with other phosphors in a light emitting device or a display device that can emit various colors of light including mixed-color light of white light. It is to be understood that although the present invention has been described with regard to prefeixed embodiments thereof j various other embodiments and variants may occur to those skilled in the art, which are within the scope and spirit of the invention, and such other embodiments and variants are intended to be covered by the following claims. 

What is claimed is:
 1. A red phosphor represented by formula (1): (x-a-b)MgO.aM¹O.bM²O_(1.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (1) wherein x, y, z, a, b, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597, 0<z<0.1, 0≦b≦1.0, 0<f2.0, 0≦g<0.484, 1.144<(x-a-b) and further, b and g satisfy b+g≠0; M¹ is at least one element selected from the group consisting of Ca, Sr, Ba, and Zn; M² is at least one element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; M⁶ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn; M⁷ is at least one element selected from the group consisting of B, Al, Ga, and In; and X is at least one element selected from the group consisting of F, Cl, Br, and I; and wherein M⁶X₂ is other than MgF₂.
 2. A red phosphor represented by formula (2): (x-b)MgO.bM²O_(1.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (2) wherein x, y, z, b, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597, 0<z<0.1, 0≦b≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-b), and further, b and g satisfy b+g≠0; M² is at least one element selected from the group consisting of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; M⁶ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn; M⁷ is at least one element selected from the group consisting of B, Al, Ga, and In; and X is at least one element selected from the group consisting of F, Cl, Br, and I; and wherein M⁶X₂ is other than MgF₂.
 3. A red phosphor represented by formula (3): (x-c)MgO.cM³O_(0.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (3) wherein x, y, z, c, f, and g satisfy 1.144≦x≦11.0; 0<y<1.597, 0<z<0.1, 0<c≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-c); M³ is at least one element selected from the group consisting of Li, Na, and K; and M⁶ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn; M⁷ is at least one element selected from the group consisting of B, AL, Ga, and In; and X is at least one element selected from the group consisting of F, Cl, Br, and I; and wherein M⁶X₂ is other than MgF₂.
 4. A red phosphor represented by formula (4) (x-d)MgO.dM⁴O_(2.5).yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (4) wherein x, y, z, d, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597, 0<z<0.1, 0<d≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-d); M⁴ is at least one element selected from the group consisting of V, Nb, and Ta; and M⁶ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn; M⁷ is at least one element selected from the group consisting of B, Al, Ga, and In; and X is at least one element selected from the group consisting of F, Cl, Br, and I; and wherein M⁶X₂ is other than MgF₂.
 5. A red phosphor represented by formula (5): (x-e)MgO.eM⁵O₃.yMgF₂.fM⁶X₂.(1-g)GeO₂.gM⁷O_(1.5):zMn⁴⁺  (5) wherein x, y, z, e, f, and g satisfy 1.144≦x≦11.0, 0<y<1.597, 0<z<0.1, 0<e≦1.0, 0<f≦2.0, 0≦g<0.484, 1.144<(x-e); M⁵ is at least one element selected from the group consisting of Cr, Mo, and W; and M⁶ is at least one element selected from the group consisting of Mg, Ca, Sr, Ba, and Zn: M⁷ is at least one element selected from the group consisting of B, Al, Ga, and In; and X is at least one element selected from the group consisting of F, Cl, Br, and I; and wherein M⁶X₂ is other than MgF₂.
 6. The red phosphor according to claim 1, wherein M² is Sc or Lu and X is Cl or Br.
 7. The red phosphor according to claim 2, wherein M² is Sc or Lu and X is Cl or Br.
 8. The red phosphor according to claim 3, wherein M³ is K and X is Cl or Br.
 9. The red phosphor according to claim 6, wherein M² is Sc or Lu and b satisfies 0<b≦0.495.
 10. The red phosphor according to claim 7, wherein M² is Sc or Lu and b satisfies 0<b≦0.495.
 11. The red phosphor according to claim 8, wherein M² is Sc or Lu and b satisfies 0<b≦0.495.
 12. The red phosphor according to claim 4, wherein M⁴ is Ta and X is Cl or Br.
 13. The red phosphor according to claim 5, wherein M⁵ is Mo and X is Cl or Br.
 14. The red phosphor according to claim 9, wherein M⁶ is Ga and X is Cl.
 15. The red phosphor according to claim 10, wherein M⁶ is Ca and X is Cl.
 16. The light emitting device according to claim 14, wherein f satisfies 0<f≦1.472.
 17. The light emitting device according to claim 15, wherein f satisfies 0<≦1.472.
 18. The red phosphor according to claim 16, wherein M⁷ is Ga and g satisfies 0<g≦0.295.
 19. The red phosphor according to claim 17, wherein M⁷ is Ga and g satisfies 0<g≦0.295.
 20. The red phosphor according to claim 1, wherein a satisfies 0.094≦a≦0.462, and M² is Sc or Lu and X is Cl or Br.
 21. The light emitting device according to claim 2, wherein z satisfies 0.001≦z≦0.049. 